Proton Magnetic Resonance Spectra of Metal Ammine Complexes. I. Cobalt(III) Pentammine Series

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概要

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• The proton magnetic resonance spectra have been measured in dimethylsulfoxide on some cobalt(III) complexes of the type [CoX(NH<SUB>3</SUB>)<SUB>5</SUB>]. Ammine protons show two peaks, except in a complex with X=NO<SUB>2</SUB><SUP>−</SUP>. The major peak, due to <I>cis</I> NH<SUB>3</SUB>, appears downfields and the minor one, due to <I>trans</I> NH<SUB>3</SUB>, upfields as compared with the shift in [Co(NH<SUB>3</SUB>)<SUB>6</SUB>]<SUP>3+</SUP>. In the case of X=CN<SUP>−</SUP>, the shift pattern is reversed. For [Co(NO<SUB>2</SUB>)(NH<SUB>3</SUB>)<SUB>5</SUB>]<SUP>2+</SUP>, the spectrum is a single peak. This chemical shift behavior is explained by a simple model based on Ramsay's theory for chemical shift. It is concluded that the behavior arises primarily from paramagnetic anisotropy of the central cobalt (III) ion. The model used in this work is shown to be applicable also to the assignment of the PMR spectra for complexes of the types <I>cis</I>-[CoX<SUB>2</SUB>(NH<SUB>3</SUB>)<SUB>4</SUB>] and <I>cis</I>-[CoX<SUB>2</SUB>(en)<SUB>2</SUB>].

• 公益社団法人 日本化学会の論文

著者

• YONEDA Hayami

  Department of Chemistry, Faculty of Science, Hiroshima University

• Nakashima Yoshiaki

  Department of Chemistry, Faculty of Science, Hiroshima University

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